Process for the Preparation of Cement, Mortars, Concrete Compositions Containing a Calcium Carbonate - Based Filler Treated with an Ultrafine Filler and a Superplasticizer, Compositions and Cement Products Obtained and Their Applications

ABSTRACT

PROCESS for the preparation of cement/mortar/concrete compositions or systems, (for simplicity hereafter “cement” compositions or systems or even “cements”), of a generally known type containing low or medium (standard) “filler(s)”, and/or optionally HP filler(s), as carbonate-based filler(s), namely coarse low or medium calcium carbonate(s), namely coarse marble(s); Product comprising, or consisting of, the pre-blend (A) of coarse, low or medium (or optionally HP) “calcium carbonate-based filler” pre-blended with at least an UF; Aqueous compositions (B) obtained by mixing the above pre-blend (A) of coarse filler(s) with UF(s) with an aqueous system such as mix water, aqueous mix fluid; Product (C) consisting of, or comprising, the pre-blend (A) or the compositions (B), treated or pretreated with at least one superplastifier or aqueous system containing superplastifier(s); Cement and Use of cement.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the field of cement compositions,cementitious compositions, hydraulic binders compositions, mortarcompositions, concrete “compositions” (or hereafter equivalently“systems”), namely of the type compositions (or “systems”) ofcement/hydraulic binders, mortars, concrete, containing at least oneparticulate mineral of the calcium carbonate(s) type as a filler, andtheir applications, as well as the corresponding cement, mortar,concrete products or elements, the said filler being a filler “upgraded”according to the invention from a “standard” level to a “technical” or“high performance” (“HP”) level of performance due to a process which isthe essential part of the invention.

The invention relates to a specific process for producing the said“compositions” or “systems” (those terms are going to be used asequivalents in this application and claims) for cement, hydraulicbinder, mortar, concrete, the obtained compositions, the cement, mortarsand concrete products obtained therefrom, and their applications.

PRIOR ART

It is reminded that a cement “system” (or equivalently “composition”) isa system comprising cement particles, mixing water (or equivalently amixing aqueous composition not interfering with the said system, asknown to the skilled man), filler(s), various optional and usualadditives such as air entrainment agents, setting retarders, settingaccelerators and the like, and any such routine additives as well knownto the skilled man.

A mortar system additionally contains an inert aggregate material,usually a sand.

A concrete system still additionally contains gravel.

The above is abundantly known and common knowledge.

Definition: cement systems or compositions or slurries: As a matter ofsimplicity, and also because the invention relates to the use ofadditives adapted to improve or “upgrade” the properties of any of thosethree systems, the terms “cement systems” (or “compositions”) (or“slurries”) (or “cements”) will be used in the following to encompassANY of the above main kinds of compositions or “systems” and theirtechnical equivalents, that is a cement, cementitious, hydraulic binder,mortar or concrete composition or system. The skilled man will be ableto appreciate if the system is a cement, a mortar or a concretecomposition in view of the presence, or the absence, of sand and/orgravel. This simplification is made possible since sand and gravel areinert materials, and therefore do not noticeably interfere with theinvention.

“Technical equivalent” means that the composition may contain “inert”components or components having about the same function and producingabout the same results: for example, a pure cement can be replaced witha cement containing cement additives, or a cementitious compositionbehaving like a cement brand, and so forth. That definition is widelyknown and understood.

It is also pointed out that, even if, in the following, an informationis provided regarding “cement systems (or compositions)” (or even“cement” for simplicity) for example, it ALSO applies mutatis mutandisto any of the above other kinds of systems (mortars, etc. . . . ). Theonly difference between the systems being mainly the presence, or not,of sand and/or gravel.

In such compositions, “bottom-tank” fluidifier(s) is/are often used. Inthat domain, the EP 0 663 892 to CHRYSO is certainly the most relevantdocument, which discloses fluidifier polymers for mineral suspensionswith no hydraulic setting, or hydraulic binders slurries.

Cited applications are paper coating, paints, and synthetic resins orrubber compositions.

According to the said prior art, it was known to add fluidifiers inmineral, particular suspensions to lower their viscosity, and,especially for paper applications, this leads to high mineralconcentrations, a better workability, and this reduces the dryingenergy. For example, this is used in connection with suspensions ofcalcium carbonate.

It is also known to add such fluidifiers to “cement” (in the wide senseexplained hereabove) slurries, with the purpose this time of reducingtheir water content and to obtain a “cement” composition with a “moredense structure” after setting.

Encountered problems are: the influence of electrolytes, which reducesthe fluidifying effect and forces to increase the amount of fluidifier(with an increase in cost), as well as, for “cement”, the need not tonegatively alter the setting characteristics of the cement compositionnot its final properties.

Some well-known fluidifiers are superplastifiers or plastifiers.

In that domain, the EP 0 663 892 to CHRYSO is relevant, as well as FR 2815 627, FR 2 815 629 and WO2008/107790 which also disclose interestingsuperplastifiers.

Some known fluidifiers affect less the setting time, but are stillunsatisfactory, such as condensation products of sulfonated naphtaleneand formaldehyde or melamine-formaldehyde with a sulfonated compound.Some of those products are also superplastifiers, but much lesspreferred.

Also, EP 0 099 954 relates to fluidifiers made by condensation ofamino-sulfonic acid comprising at least an aromatic ring withnitrogenated compounds bearing several amine functions and formaldehyde.

Such are said not to delay too much the setting of cement compositions,but they are highly sensitive to electrolytes when it comes to their“activity”. They also can be obtained with low concentrations, usuallyno more than about 40% to by dry weight, since any concentrationincrease in turn increases their viscosity to inadmissible levels.

The summary of the desired properties is listed page 3 lines 15 ff ofthe above-mentioned EP.

It is also known to add filler(s) in cement, hydraulic binders,cementitious or concrete or mortars compositions or “systems”.

The purpose of adding such filler(s) is to fill the voids betweenparticles, to reduce the overall costs, to greatly improve a propertycalled “consistency” (consistency being the capacity or ability for theconsidered systems to easily flow or “self-level”, or not) and toimprove a property called “compacity” (that is the percentage of drymaterial in the final composition (the higher the percentage, the betterthe compacity)).

Finally, EP 10 008 803.8 describes the treatment of calcium carbonatebased filler(s) (see definition herebelow) with certain superplastifiersoptionally admixed with certain plasticizers and optionally fluidifiersin order to upgrade “low” or “dry” grade (or “standard”) “cementsystems” (not usable in the modern industry as explained in detail inthe said application and herebelow for completeness) to at least“plastic” and most preferably “fluid” “cement systems” which can be usedwith great advantages in the modern industry.

In the above considered prior EPA, a true “treatment” is performed”,leading to a definite and surprising technical effect.

Definition: calcium carbonate-based filler(s): In the said previous EPapplication cited just above, as in the present application, the saidusable filler(s) is/are defined as “calcium carbonate-based filler(s)”that is, in the application and claims, coarse fillers that contain(s)only calcium carbonate(s) (possibly of various origins, such as variousnatural rocks GCCs or various PCCs) which means with no other filler ofa different type, such as kaolin, bentonite, etc. to known to theskilled man, and is/are preferably provided (when the filler(s) is/areor contain(s) GCC(s)) by a carbonated rock or more generally mineralmaterial(s) comprising at least 50-65% by weight (dry) of CaCO₃,preferably more than 80%, still more preferably more than 90%; thosefiller(s)s are selected among:

-   -   natural calcium carbonate(s) or ground calcium carbonate(s)        (GCC(s)) such as, non limitatively, GCC from marble, chalk,        calcite, or from other natural and well-known forms of natural        calcium carbonates which preferably meet the above % criteria;        -   PCC(s) which is a precipitated calcium carbonate, and exists            under various well-known forms, depending on the well-known            precipitation/preparation process.        -   or a mixture of said CaCO₃-containing rocks or mineral            materials with each other as well as blends or mixtures of            GCC(s) and/or PCC(s).

The GCC/PCC ratio can be chosen from 0-100 to 100-0% by dry weight,preferably from 30-70 to 70/30% by dry weight.

Usually a “filler” has the following properties:

-   -   Purity (methylene blue test) is lower than 10 g/kg, preferably        below 3-5 g/kg, preferably below 1-1.5 g, with a most        interesting value at 1.2 g/kg. See NF P 18-508 2012-1 4.2.6        refering to NF EN-13639.    -   Mean diameter or d₅₀ is about in the range of 1-3-5-6 to 30-50        micrometres measured by using the Malvern 2000 PSD        equipment/methodology or Sedigraph.

See the above NF P 18-508 4.3.2.

As will be seen below, the d50 range of about 1-5-6 microns corresponds,for the fillers featuring a Blaine surface above about 1000 m2/kg, toultrafine fillers (UFs); d50 above 6 microns is the domain of coarser orcoarse fillers, hereafter “fillers”. In this application, when ultrafinefillers are considered, the wording “ultrafine” or “ultrafine fillers”or “UF” will be used.

-   -   Blaine surface, which is a characteristic feature of fillers, as        is well-known, is in the domain of 180-2000 m²/kg, preferably of        300 to 800 m²/kg, as measured under an EU Standard (European        standard EN 196-6).

As discussed above, UFs have a Blaine surface above about 1000 m2/Kg inaddition to a d50 below 5-6 microns.

-   -   The above definition of “calcium carbonate-based filler(s)” is        also valid in the present application, though the present        invention uses the said fillers in a synergy: such coarse        calcium carbonate based filler(s in admixture with an ultrafine        filler (“UF”) and at least a superplasticizer as explained        herebelow.)

As is known, a “cement” (in the above mentioned wide sense) compositionor “system” is mainly made of:

Cement (or cementitious composition or hydraulic binder)+mixing water(or mixing aqueous composition allowing setting but not interfering withthe system)+optionally (usually inert) particulate and/or fibrousfiller(s)+inert agglomerate(s) such as optionally sand+optionally inertgravel (plus optionally well known additives not to be mentioned indetail nor in full in the present application, such as settingaccelerators, setting retarders, air entrainment agents, etc. . . .)+miscellaneous “routine” additives aimed at matching the precise needof the end-user.

Aggregates such as sand, inert gravel or “all-in” aggregates are knownmaterials so commonly used that no description is needed here.

As discussed above, the invention relates also equivalently (under thegeneric term “cement” for simplicity) to mortars compositions or“systems” (like above including an aggregate like sand but no gravel)and cement compositions (same as above but no gravel and no sand).

“Mainly” means here that the system may contain some impurities ortraces of additives or adjuvants, not to be mentioned in the presentapplication, such as air entrainment agents, accelerators, retarders,etc.

“Mixing water” will mean in this patent application plain mix water oraqueous mixing compositions, that is mainly water plus usual additives,allowing the normal setting of the “cement” compositions, withoutinterfering with the other properties of the overall composition, oronly, via the additives, to improve some usual properties.

“Filler(s)”:

In this invention “filler(s)” means coarse “calcium carbonate basedfiller(s)” which have been precisely defined hereabove, that is fillerscontaining under any known form (namely GCCs and/or PCCs), only CaCO₃particulate material, plus optionally some other inert filler particlesor fibrous material such as hemp etc. . . . . We remind here that inthis application, “fillers” means “d50 above 6 microns” that is coarsefillers.

It was not disclosed in the above quoted EPA to treat such a “filler”with at least one ultrafine filler (hereafter “UF”) since there existeda strong prejudice against mixing a coarse filler with an UF. Actually,the then predictable result of such a blend would have been anunworkable mix of coarse and ultrafine particles that could lead only tosome undefined “mud” instead of a workable slurry. Actually the expecteddifficulties have been encountered but overcome by further R&D work andthe above mentioned synergy with a superplastifier.

In this whole application and claims, “inert” shall mean a materialwhich has no noticeable (or negligible) impact or interference with theprocess of the invention and the obtained compositions, products andapplications. Given the involved ingredients, this will be easilyappreciated by any skilled man.

The prior art “cement” (in the wide sense as defined above) systems todate are therefore mainly made of:

Cement (or hydraulic binders or cementitious compositions)+mixing water(or mixing aqueous compositions not interfering with thesystem)+optionally aggregate(s) such as sand+optionallygravel+fillers(s)+“routine” additives. In the prior art, “filler(s)means coarse filler(s), never a blend of coarse filler(s) and UFfiller(s).

It is also known that cement/hydraulic binders/cementitiouscompositions, cements, mortars and concrete compositions can bebasically sorted out into:

DRY systems (poor quality or “low”) (casting is performed with highvibration and energy).PLASTIC systems (medium quality) (medium vibration and energy). (The twoabove categories may also be named “standard” by the skilled man).FLUID systems (High performance or “HP”) (low vibration and low energy).(The “fluid” or “HP” systems are also named “technical grade” by theskilled man)

This categorization remains valid in the present invention as well asthe herebelow test.

A very simple test is used to classify the systems, using a “mini cône àchape” known as “self-levelling test” or “screed flow cone test”.

The test is well known and is conducted as follows, according to therecognized Standard EN 196-1; the said standard defines accurately themixer or kneading (also malaxing) device to be used, the speed ofrotation, and each and every such data useful for reproducing the test.Therefore, no more explanations or definitions are needed here for thesake of clarity or reproducibility.

For simplification, we remind here that “cement” will encompass in thiswhole application not only cement material, but also cementitiouscompositions and hydraulic binders (other than cement) compositions, andtheir blends and technical equivalents. As indicated above, it alsoencompasses corresponding mortars and concretes.

Self Levelling Test:

Basically, a cement or mortar or concrete “system” is prepared by mixingthe above ingredients according to usual practice, recalled here-belowin more detail though the process conditions are well known, then ispoured in accordance with the above Standard conditions, into aninverted cone which is perforated at its bottom (dimensions are alsogiven by the said Standard as well as each and every useful data of thetest).

The cement or mortar or concrete system therefore flows into and out ofthe said cone, namely through its bottom aperture, and falls onto anhorizontal plate to form a “chape” (“screed”).

It there forms a “galette” or “cone spread” also known as “dry toplastic or fluid form” which “spreads” and whose diameter is measured,and whose aspect is separately visually inspected for example forstickiness and “thickness”, and “flow speed”, etc. . . . ; the latterproperty when “thick” or sticky” or “pasty” or “low flow” reflecting a“slow” or “viscous” mix, that is, especially if “thick”, or worst “dry”,hard to handle. To the contrary, a high flow speed and a fluid aspectcorresponds to a nicely workable product, of the “FLUID” type.

The larger the diameter, the more flowable the system. For a given highconsistency, as targeted by the invention, this is the major test.

Given the quality of the initial filler to be used in the concretesystem, namely its place of production, morphology etc. the resultingcone will vary in diameter, this indicating a variation in flowability.Attention has also to be paid to the “cone” used, which plays a role inthe obtained diameter. All this is abundantly known to the skilled man.

As an example, a GCC which is known to use no or almost no mixing water,and shows such valuable properties, will lead to a very fluid, nonsticky cement or concrete composition. Such a composition will be fullyusable for “technical” (that is, “high performance” or “HP”) concretecompositions, called “FLUID” above.

If to the contrary, the filler namely GCC filler absorbs or uses anoticeable amount of water, or contains some impurities, etc. theresulting composition will be less fluid and become to be somewhatsticky. The end user will be forced inter alia to either add acorrective adjuvant (with an associated extra cost and an associatedrisk of secondary effect of the composition as a whole) and/or add extrawater (thus being detrimental to consistency and inducing associatedrisks). Those compositions will be used for medium quality compositions,called “PLASTIC” hereabove.

At the other end of the ladder, using a filler namely a GCC of poorquality will lead to a composition which will exit the mixer under theform of sticky granulates. Those will be used only for DRY concretecompositions, NOT part of the invention.

The test will be sufficient for a skilled man to rate the starting GCCand/or PCC (s).

The same is valid mutatis mutandis when using a PCC or a GCC/PCC blend.In order to provide the skilled man with useful guidelines andinformation about the meaning of “low”, “medium” or “HP” filler, weattach the TABLE A where ten fillers A to K of various origin andmorphology (as indicated for characterization by the skilled man) havebeen tested for various properties and qualities, or drawbacks, with theclassification “low” “medium” or “HP” being added on each line.

We also attach the TABLE A BIS which defines the time ranges a mixtureis considered low medium or HP and the corresponding times for theV-funnel test. This TABLE A BIS shows the ranges which define the lowmedium and High performance mixtures. Due to the ranges 30-120 sec,10-30 second and <10 second the skilled person easily can recognize inwhich part of the ranges his mixture is i.e. in- or out-side and how toadapt accordingly.

The contributions of the microfiller to the rheological properties ofthe mortars were measured by slump flow with a mini cone and flow timethrough a V-Funnel. Table A BIS shows the microfiller performanceevaluations for concrete. There in the Experimental methods * the LG16test is described as well as the Slump flow and flow time, and thegeometry of V-Funnel.

It is referred in the present application to standard NF EN-934-2 whichdefines the role of adjuvants. Reference should be made also to standardNF EN 206-1 which among other refers also to the 28d compressionresistance and to EN 197-1:2000 defining “aluminosiliceous” materials insections 5.2.3. and 5.2.7, as well as standard EN 18-508 definition of“UF” in 4.3.2.

TABLE A Characterization of “low”, “medium”, “HP” fillers and theiraspect Treatment Blue Agent geological (Methylene visual Codedesignation (age) Type d50 Blaine Blue Test) (3 g) (4 g) Evaluationevaluation A white chalk facies chalk 1.0 >1400 2.0 plastic 220 lowslow, very (90 Mi) aspect thick B white chalk facies chalk 2.2 1120 2.7280 340 medium thick (90 Mi) C urgonian facies calcite 3.1 1171 0.3 200290 low slow, thick (115 Mi) D bioclastic facies calcite 6.0 720 1.0plastic 338 medium plastic (160 Mi) aspect E urgonian facies calcite 6.5395 0.3 460 475 HP fluid (115 Mi) G upper jurassic marble 17.0 363 0.3dry 365 medium slow, heavy (130 Mi) aspect H upper jurassic marble 13.4385 0.3 337 413 low slow, viscous (120 Mi) I H + 5% B X X X X 190 390medium slow, viscous J H + 15% B X X X X 427 436 HP fluid K H + 20% B XX X X 340 410 medium fluid, thick

TABLE A BIS Low medium HP A C H B D G I K E J 3 g plastic 200 mm 337 mm280 mm plastic dry 190 mm 340 mm 460 mm 427 mm slump flow 4 g 200 mm 290mm 413 mm 340 mm 338 mm 365 mm 390 mm 410 mm 475 mm 436 mm V-funnel 4 g30-120 sec 10-30 sec <10 sec flow time time 82 54 66 28 20 17 24 15 6 8

One uses 3 g or respectfully 4 g of fluidifier Premia 196™commercialized by the Firm CHRYSO, which acts as a routine “bottom-tank”fluidifier and which is a commercial product at a concentration of 25.3%by weight (dry extract measured along the Standard EN 480-8), by DRYweight of cement.

In the said Table A, “+15% B” evidently means an addition of 15% of theproduct B, to form a blend or mix, the % being in DRY WEIGHT/DRY MIXWEIGHT.

Equally, columns “3 g” and “4 g” means that 3 or respectfully 4 g of thesaid routine fluidifier have been added by DRY weight of the cementcomponent alone. In the following this product will be named accordingits routine function, that is “fluidifier”. The skilled man knows thatsuch a fluidifier is routinely added in the “bottom” of the kneadingtank when preparing a cement composition.

“Mi” means “million years” (dating of the rock)

“Blue” means “methylene blue test” (purity test)

This introduction of this application clearly points out to the need forimproved cement or mortar or concrete systems or compositions having aimproved compacity (% of dry material, the highest possible), animproved flowability (that is forming a fast or relatively fast-flowingcomposition, non sticky “galette” or “cone spread” (more simply “cone”or “cone diameter”) of large diameter in the above described test, thelarger the diameter, the better flowability), and globally speaking adefinitely improved “workability” (workability being the ability of thecement or concrete composition to be prepared, processed, handled, andused to form a high performance or “technical” concrete) and a farbetter “regularity” in the final product properties especially at theend user level.

Clearly, some of those desired properties are antagonistic, and forexample one should expect a high % dry material to perform poorly in aflowability test.

Technical Problem(s) to be Solved

The main purpose of this invention is to build a process aimed atproviding improved, “High performance” (or “HP”), FLUID, cement ormortars or concrete systems or compositions having an improved compacity(percentage of dry material, the highest possible), an improvedflowability (that is forming a non sticky “galette” or “cone spread” oflarge diameter in the above described test, the larger the diameter, thebetter to flowability), and globally speaking a definitely improved“workability” (workability being the ability of the cement or concretecomposition to be prepared, processed, handled, and used to form a highperformance or “technical” cements, mortars or concrete compositions orsystems),

-   -   using as “filler(s)” (in the general and global sense)    -   at least a coarse, “low” or “medium” (or optionally HP)        carbonate-based filler treated first with an UF (ultrafine        filler),    -   the resulting blend (or fillers blend or preblend) being then        treated with at least one superplastifier.

The process will be conducted routinely in the presence of a smallamount of a fluidifier.

Another property, which does not exists in the prior art, while theindustry is strongly demanding it, is “regularity” of the properties ofthe final systems. In some cases, one can accept a cone diameter near tothe 300-350 mm range, if the filler is particularly “difficult” toupgrade and if this allows a purely mineral solution to be implemented.The skilled man knows how to design such compromises.

It has been surprisingly found according to this invention, that thatset of objectives can be reached by treating the low/medium (or“standard”) “filler(s)” in the specific manner as disclosed below, withan UF then by treating this pre-blend with only minute amounts oftreating agent(s) (superplastifier(s)), and with a very impressivetechnical effect.

BRIEF SUMMARY OF THE INVENTION

The invention resides first in a:

PROCESS for the preparation of the above defined cement/mortar/concreteto compositions or systems, (for simplicity hereafter “cement”compositions or systems or even “cements”), of a generally known type asdefined hereabove containing low or medium “filler(s)” (carbonate-basedfiller(s)), namely coarse calcium carbonate, namely coarse marble(s),characterized in that it comprises, or consists of:

-   -   at least one first step where the said low or medium “fillers”        is/are treated with an efficient treating amount of at least one        UF, what forms the “fillers pre-blend”, and    -   at least one subsequent or second step where the resulting        “fillers pre-blend” is treated with a treating agent consisting        of or comprising at least a superplastifier.

The process will be conducted routinely in the presence of a smallamount of a “bottom-tank” fluidifier.

The two steps may be separated by some additions of routine, inertadditives as is known in the art. They are preferably not separated bysuch intermediate steps so as to take full benefit of the synergy withthe superplastifier treatment. Each treatment step with an UF or thesuperplastifier may be fractionated, though it is preferable (forpractical reasons, nature of the available equipment on site etc. . . .) that they are not.

“Ultrafines particles” or more simply “ultrafines” or still more simply“UFs” which can be used in the present invention can be defined by

-   -   a d50 from about 1 micron to about 5 or 6 microns, preferably        from 1 to 3 microns, and still better of about 2-3 microns,        usually <5 microns.    -   and    -   a high specific surface, usually defined as BLAINE>1000 m2/kg        pref.>1500 m2/kg, pref. up to 2000 M2/kg.    -   Reference can be taken as to CaCO3 additives (“additions        calcaires”) to a cement from NF P 18-508 (2012-01), see 4.3.1        (Blaine) (NF EN 196-6) and 4.3.2 which defines the “Highly Fine”        additives as having namely a d50<5 microns; which also refers to        the “bleu de methylene” test (NF EN 13639)(4.2.6) and other        interesting definitions.    -   Quite representative examples of such useful UFs are:    -   silica fumes (d50=about 1-2 microns),    -   such as Condensil S 95 D d50=1.2 microns, Blaine>1500 m2/kg BET        (specific surface area measured using nitrogen and BET method        according to ISO 9277) BET=16 m2/g    -   metakaolin (that is calcined kaolins, d50=about 3 to 5-6        microns) such as Premix MK™ d50=3 microns, Blaine=3.8 m2/g    -   chalks of d50=about 1 to 5 microns d50,    -   calcites of about 1 micron d50,    -   Millicarb™ OG white limestone Orgon, France, (about 3 microns        d50),    -   marbles of about 1 to 5-6 microns d50,    -   Durcal™ 1 or 2 white marble from Salses, France (d50 1 resp. 2        microns),    -   “Etiquette violette” (“EV”) microcrystalline Champagne Whiting        from Omey, France (about 2.4 micron d50),    -   Ultrafine siliceous product (Sifraco™ C800 d50: 1.86-2.4 micron        BET=2.7 m2/g)    -   PCCs (precipitated calcium carbonates) such as of d50=1.52        micron Modified calcium carbonates (or “MCC”) such as of        d50=2.29 microns, in particular those disclosed in U.S. Pat. No.        6,666,953.

When Blaine surface is not indicated in the present application, thisonly means that the standardized test is not adapted to the fineness ofthe considered product and/or to its morphology, as is known to theskilled man. to Those products however meet the Blaine surface criteriaor very high specific surface as reminded above.

Preferred UFs to be used in the present invention are: EV™, silica fumeSF, metakaolin MK, DURCAL™ 1 or 2 and their mixtures.

Modified calcium carbonates (MCC) and PCC can also be used as UF(s).

For completeness, one can say that when the d50 is above 5-6 microns onestarts to regard the products as “fillers” not “UF” s any longer.

In the following, the wording “pre-blend of filler+UF” (or equivalently“fillers pre-blend”) will therefore mean a pre-blend of at least a“filler” (low or medium) (or optionally HP) which is coarse (d 50>6microns, usually, as is known, clearly above 6 microns) with at least aUF (d 50<5-6 microns), preferably ONE filler with one or a “mix” of twoUFs.

The low-medium fillers which are used in the invention are coarsecalcium carbonate(s) based filler(s), namely calcium carbonates ofvarious origin such as marbles etc. . . . and their blends, see theabove definition, and can be optionally mixed with “non interfering”fillers, and with “non-interfering” routine, inert, “adjustment”additives.

Evidently, some HP fillers can be also upgraded with the presentinvention, though they are already HP fillers.

The said “treatment” of the filler(s) particles with the UF particles asmentioned above is performed by a mere mixing or blending.

It is quite surprising to notice that this mixing of coarse particles offillers with UF particles leads to a “workable” product such as a cementcomposition or slurry.

The general knowledge of the skilled man was that such a mix would leadto a mud-like, pasty, etc. . . . mixture, that is a definitelyUNworkable and UNusable slurry. One merit of the inventors is to haveovercome that solid prejudice.

-   -   It is surprising to note that such a filling (“remplissement”)        of the voids between the coarser or coarse carbonate-based (low        or medium) fillers particles with the ultrafine particles of the        UF(s) instead of producing as expected a solid and strong mass        of particles (due to the reduction of the interparticles voids        and therefore the “compacting” of the whole mass), produces to        the contrary an Unblocking effect and an upgrade effect from        low/medium (standard) to HP/technical/fluid fillers.    -   As mentioned above, the second prejudice which the invention        overcomes is that, when mix water is added, the said blend of        low/medium fillers with UF(s) does not produce as expected a mud        or pasty cement composition that would be Unworkable, but to the        contrary a workable, non pasty, non sticky, cement composition        with a large “galette” diameter in the “cone test” or        “self-levelling test”.    -   It is probably because one expected that the voids to be filled        with UFs would create a solid and strong mass of compacted        particles that one believed that no dispersion would be possible        so that when adding mix water, a mud or pasty product would have        to be expected. So the two prejudices overcome by the present        invention were actually interconnected with each other for a        skilled man, therefore creating a very solid (because very        coherent) prejudice.

In the above, “interparticles” has to be understood as globally all thekinds of particles present in the “cement” system: it can be mainlyhydraulic binder and filler (coarse and UF) particles in case of acement composition, or the same plus sand in case of a mortar, or thesame plus sand and gravel (or any sort of know “aggregates”) in the caseof a concrete.

It is equally surprising to note that the treatment of the fillerspreblend with superplastifier(s) a) is possible and b) provides animportant technical effect: one would have reasonably expected that thefilling of the voids between the coarse particles of fillers with the UFparticles would have either made most of the particle surfacesUnavailable for any chemical treatment, and namely any surface treatmentsuch as ionic etc. . . . or would have restricted the chemical treatmentto the only portion of the particles being directly accessible to thetreating superplastifier or even that the said superplastifier wouldhave acted on the per-blend in such a way as to block it (this becauseit is already surprising to blend coarse and UF particles withoutproducing a mud-like system, so additionally mixing a chemical agent wasevidently adding to the risk of destroying that unexpected fluidity ofthe pre-blend).

The tests performed on marbles are particularly surprising.

The treatment with the superplastifier!s) is believed to treat only thecalcium carbonate(s) part of the filler(s), and for example not theother particulate or fibrous fillers, IF ANY, believed to be inert inthis process.

By “comprising or consisting of” we mean that the starting low-medium(or optionally already HP) fillers may consist of calcium carbonate(s),optionally mixed with non interfering fillers, and that the treatingagent(s) can be: only superplastifier(s) or blends of superplastifier(s)with non-interfering plasticizer(s) (as defined herebelow) and/orroutine, inert, additives.

As to the treating UFs they are as described above and may also containnon-interfering amounts of “inert” fillers”.

By “efficient treating (or “treatment”) amount” or “efficient surfacecoverage of the fillers particles or grains” or “efficiently treated”,we mean in this application that at least 50%, preferably at least 60,or better at least 80 or 90% or still better closer to 100% of thesurface of the particles of the filler(s) (that is the low or mediumfiller preblended with an UF) have been subjected to a physico-chemicalinteraction with the superplastifier(s). This physico-chemicalinteraction is not entirely understood as of the filing date, only theEFFECTS and RESULTS are duly identified and correlated to the treatingsuperplastifier(s), but, without being tied by any theory, the applicantconsiders that the said interaction or “treatment” is a surfacetreatment or “surface-covering” treatment involving ionic, physical,mechanical and/or chemical, treatment(s) and via said interaction(s).This efficient treating or treatment amount must therefore be importantenough to treat the said % of particle surfaces, as will be explainedand disclosed in more detail below.

It is surprising to consider that the said treatment is efficient eventhough the fillers contain coarse and UF particles, and that theto-be-expected mud does not form during the treatment, nor during thefinal preparation of the cement composition.

By “surface-covering” we mean that the superplastifiers are supposed bythe applicant, without being tied by a theory, to engage in electricalcharge potential interactions with the ionic charges of the surface ofthe (low/medium filler+UF) pre-blend, which promotes the fixation of thesuperplastifier onto and/or closely around the surface and so reducesthe “accessible” surface of the particle having no surface saturation ofthe grain by said treatment.

This corresponds to an “UNblocking” of the particles or grains, whatfirst “triggers” then promotes the mobility freedom of the particleswith respect to each other.

This is NOT a fluidification process: this is a “trigger action” leadingto an UNblocking process or sudden removal of interparticleinterference/friction without which the rest of the properties cannot bereached and especially not the required fluidity.

It is believed that this so “triggered” “Unblocking” function is one ofthe very key parameters allowing to appreciate the appropriate“treatment” or “surface coverage”.

By “comprising” we mean in this application that the chemical treatingagent of to the “fillers pre-blend” can be made only ofsuperplastifier(s) (one or more mixed together, preferably one) or ofblends of superplastifier(s) displaying mutual non-interference (thatis, unable to noticeably degrade the above “treatment”) amount orproportion of known plasticizer(s) for the purpose of cost-saving, asexplained in greater detail here-below.

As will be seen in the examples, it is equally surprising to note that asynergy develops between the “fillers pre-blend” and the treating agent(superplastifier(s)).

Process Options are as Follows:

1 According to the best mode of the invention, as defined to date, thesaid fillers pre-blend (coarse, low or medium fillers)+UF(s)) isefficiently treated with the superplasticizer before being introduced inthe kneading or mixing device (“pre-treatment” also named “initial”),such as in an outside mixing Laboratory equipment; in the industrialscale, such a pre-treatment can be performed in an industrial devicesuch as the Lödige mixer or any other industrial kneading or mixingequipment known to the art.

2 According to a less preferred embodiment, the said fillers pre-blendis treated with the superplasticizer after having being introduced inthe kneading or mixing device (“inside treatment”). In such a case, itis preferred that the filler(s) and the efficient treating amount of thetreating agent(s) (superplasticizer(s)) be introduced in the kneading ormixing device either simultaneously or in a manner such that thefiller(s) and the efficient amount of the superplasticizer treatingagent(s) are introduced separately BUT at a very close location andtime.

3 According to another embodiment, the said fillers pre-blend isefficiently treated partially before being introduced in the kneading ormixing device (“partial pre-treatment”) (such as in a well-known Lödigeequipment) and partially after having been introduced in the pre-treatedstate in the said mixing or kneading device, the total of the twopartial treatments being “efficient” in terms of treatment, surfacecoverage etc. as defined above. It is preferred to operate with thesecond part or amount of the treating agent(s) being introduced in thekneading or mixing device either simultaneously with the pre-treatedfillers pre-blend or in a manner such that the pretreated fillerspre-blend and the second part of the treating agent(s) are introducedseparately BUT at a very close location and time.

When the fillers pre-blend is to be treated at least partially insidethe kneading or mixing device, (“mixed treatment”), the skilled man willunderstand that a corresponding amount or proportion of treatingsuperplastifier(s) has to be added directly into the said kneading ormixing device or in admixture with the considered filler pre-blend justbefore the introduction in the kneading or mixing device, in the lattercase, for example, by introduction on the weighting device (“balance”)which is provided just before the powdered products are introduced intothe kneading or mixing device. “Just before” will be easily understoodas a place and time where the fillers pre-blend and treating agentscannot or have no time to be mixed together, what would induce thebeginning of the treatment. A good example is the balance where the twopowders are placed together then almost immediately introduced, with noprevious kneading or mixing, into the kneading or mixing device.

It is much preferred that the point and time of introduction of the saidproportion of treating agent be as close as possible to the point andtime of introduction of the partially treated filler(s), so as not to bediluted in the pre-existing products already present in the mixing orkneading device (such as sand, gravel, mix water, optionally routineadditives, so that the treating agent be fully available for the fillerspre-blend.

This is also true in relation with the option “inside treatment”.

In both options, actually, if the fillers pre-blend is added at alocation and at a time too far form the location and time of thetreating agent, whatever the order of introduction, one could shift to atreatment which would be too late: this would actually make possible forthe treating agent to be “consumed” by other ingredients before thefiller is introduced, or, in the case of a filler introduced first, leadto a late treatment that is the “post-ajout” mode (“post-addition” ofthe superplastifier treating agent(s) a certain time after the fillerspre-blend has been introduced; one can see that the results of that modeare far lower than with a pre-treatment, a mixed treatment or an insidetreatment according to the invention.

Any post ajout has to be avoided.

The invention also covers an industrial option characterized in that atleast a portion of the efficient amount of treating superplastifier(s),or the totality of the said efficient amount, is mixed with the fillerspre-blend on the weighting device (“balance”) leading to the kneading ormixing device. This can be regarded either as a simultaneous addition,or a “near-simultaneous” addition.

Some of the above options are evidently complicated and/or requireadditional equipments or modifications of the existing equipment. Theyare therefore far less preferred, the “pretreatment or initial modebeing the most preferred. The “best mode” to date to avoid thosedrawbacks is clearly to prepare a pre-treated fillers pre-blend (thatis, pre-treated with superplasticizr(s)), then to deliver it to the enduser and to introduce it as such into the kneading or mixing device,most preferably after the mix water and sand and gravel, if any, havebeen introduced and allowed to be successively malaxed or kneaded as isusual in this industry (the difference being that, in the presentinvention, the fillers pre-blend (low or medium carbonate based fillerpre-blended with UF) is TREATED, while it is NOT in the prior art, whereadditionally there is NO UF). As discussed above, it will be pureroutine for a skilled man to perform a few self levelling tests, whichare perfectly known to him a require no costly or voluminous equipment,and no “daunting task”, so as to adapt the “efficient” dosage of thetreating UFs) vs. the filler(s) and/or to define the moment thetreatment can be stopped.

The invention also covers such a

-   -   A pre-blend of coarse, low or medium (or optionally HP) “calcium        carbonate-based filler” pre-blended with at least an UF as a new        industrial product (as mentioned above, such a blend of coarse        and UF fillers was not supposed to be possible, and was expected        to lead to a mud like product when mixed with aqueous mixing        fluid so that it is novel and surprising to design such a        pre-blend, knowing that such a mix would be thereafter        impossible to segregate again)    -   B the aqueous compositions obtained by mixing the above        blend (A) of coarse filler(s) with UF(s) with an aqueous system        such as mix water, aqueous mix fluid, as a new industrial        product    -   C the blend (A) or the compositions (B) which have been treated        or pretreated with at least one superplastifier or aqueous        system containing superplastifier(s), as a new industrial        product,    -   A, B or C being able to be delivered to the end user that way,        optionally after any treatment allowing to ease the        transportation and/or addition of routine, inert additives.

It is known, in Laboratory trials, and due to the small volumes or loadsinvolved, to sometimes first place some small amount of “fluidifiers” inthe bottom of the laboratory mixing device: some of those fluidifiersmay be superplastifiers, many are not. However, even when some smallamounts of superplastifiers—“fluidifiers” are present, they cannot“treat” the fillers pre-blend “efficiently” as in the invention, that isaccording to the definition given hereabove. They merely act asfluidifiers, so that they interact mainly with the other firstconstituents of the load, such as sand, gravel, mix water etc., whichare malaxed together, alone, for a given period of time, so as toconveniently fluidize the particles or aggregates in the suspension; inthis operation, they are “fixed” or “consumed” by the said aggregatesparticles that precisely need to be fluidized. If they were not, therewould be no fluidification. Therefore, they are then no longer availablefor the fillers; even if, to be absolutely complete, we assume for asecond that some (mandatorily very small amount) such fluidifier werequite partially and quite marginally available, it could only quitemarginally interfere with the fillers pre-blend, that is in any caseabsolutely not with as a result the “efficient” treatment effect or“surface coverage” effect or “unblocking” effect generated by thesuperplastifiers deliberately added in the present invention at a momentand at a time such as to reach the point of “efficient treatment”.Simply, the necessary “threshold” or “TRIGGER” for UNblocking could notbe reached by far, and, with no “trigger”, there could be no“Unblocking” at all.

No prior art ever reported any improvement or upgrading which might havea relation with the fluidizers (many of fluidizers being additionallyjust plastifiers, not superplastifiers); no doubt that, especially in anR&D Laboratory, if such an upgrading had been noticed, it would havebeen reported. This is simply because the “trigger” effect for“unblocking” never occurred.

In the industrial scale, one most generally uses NO fluidifiers, or insome exceptional cases in minute amounts, and in order to “fluidize” themix: there again, the fluidifiers are “used” to fluidify sand, gravel,etc. and are not available for the fillers, and therefore can in no way“trigger” the “unblocking” of the to system, the essential part of theinvention.

As indicated hereabove, the said low or medium filler(s) are made ofcalcium carbonate(s) or blends thereof, that is mainly GCCs or PCCs orblends of GCCs or blends of PCCs or blends of GCCs and PCCs.

Non limitative but appropriate of low/medium carbonate) based fillersare:

Betocarb™ EC or SL d50=9, resp. 7 microns Blaine=690, resp. 462 m2/gOmyacarb™ 10 PB or ES origin Mexico d50=about 10.8 resp. 10.4Betocarb™ SL from Salses, France d50=18 microns Blaine=365 m2/g

The invention also covers the said

-   -   “CEMENT COMPOSITIONS” (in the wide sense defined above)        incorporating (A) or (B) or (C) above, and namely incorporating        the said pre-blend of low or medium filler(s) treated        subsequently with at least one superplastifier,        -   and their USE in any “cement” industry,        -   and in the “CEMENT ELEMENTS or PRODUCTS” so obtained from            the said compositions, —and the USE of such Cement elements            or Products in the “cement” industries.

By “CEMENT ELEMENTS or PRODUCTS” it is meant in this whole applicationeach and any piece of building or construction (or any piece or productfor any other industrial purpose known to the skilled man, includingoff-shore cementing, or oil wells cementing, using “cement”compositions) such as blocks, etc. . . . , prepared from the saidcompositions.

By “cement” industries, we mean here any industry where the aboveproducts are known to receive a useful application, such as the buildingand construction industry, oilfield or geothermal cementing industry,and any such industry to evidently known to the skilled man.

This will be detailed herebelow.

“Setting time” in this application, when mentioned, will be understoodas established under Standard EN 196-3.

DETAILED DESCRIPTION OF THE INVENTION

In a detailed and most preferred (“best mode” as of today) embodiment,the said PROCESS for preparing the said “cement” compositions or systemsis characterized (in the so-called “pre-treatment” or equivalently“initial” mode) by the fact that it comprises or consists of:

-   -   a) providing a powder of dry, coarse, low or medium (or        optionally HP) calcium carbonate filler(s) as defined above as        “calcium carbonate(s)-based filler”, hereafter “filler or        filler(s);    -   b) mixing the said filler(s) with an efficient treating amount        of at least one ultrafine filler or “UF”, thus providing the        “fillers pre-blend” (of low or medium filler+UF)    -   c) mixing the said fillers pre-blend with at least one        superplastifier, thus producing “pre-treated (or “treated”)        fillers pre-blend”,    -   d) introducing the said pre-treated (or “treated”) fillers        pre-blend into a kneading or mixing device already containing        mix water or a composition of mix water possibly containing        routine or “non-interfering” additives (“mix water or aqueous        mix composition”) (hereafter for simplicity “mixing water”)    -   e) optionally adding before or after the step c), preferably        before, aggregates such as sand and/or gravel, and possibly        other “non interfering” routine additives or adjuvants,    -   f) kneading or mixing the said load during an efficient period        of time,    -   g) recovering the said “cement” composition.

By “not interfering”, it is meant not interfering or not noticeably withthe said considered treatment or inventive process.

By “efficient period of time”, it is meant a total period of timeleading to an homogeneous mixture or blend, in the order of 2-15 min,preferably, for the “standard” mixtures or blends, 30-60 s. This will bedetailed hereafter. An example of end-user application is as follows: ifthe end user targets medium or “standard” properties for its finalcement composition, for example with a final mixing within hisfacilities in a fixed installation etc. . . . , he will use compositionswhich are correspondingly simple that is not specifically complex orsensitive in terms of routine additives, superplastifier, filler etc. .. . ; therefore, the end user will have to mix for a relatively shorttime such as the above 35-65 s.

If to the contrary the end user targets high-level or very HPproperties, he will use correspondingly more complex compositions andmore sensitive components, for example a more sensitive filler orsuperplastifier, or sensitive routine additives aimed at reaching aspecific property, etc. . . . and usually he will use less or far lessmixing water: therefore he will need to mix for a much longer time suchas the above 1-3 to 10-15 min.

Evidently, “technical” composition or system means a “HP” quality (seethe “Self levelling test” section above) or “FLUID” see above too, andby contrast a “standard” final composition means a “non-HP” quality,that is, see above, “dry” or more likely “plastic”.

In both cases, that is “technical” or “standard” compositions, and asexplained in the present application, the common objective is to reach ahomogeneous composition, also as explained specifically in the presentapplication, see below “The main essential criteria final product mustbe homogeneous”.

The above working principals are well known to the skilled man and arefor completeness only. The above values and examples are to provideguidelines only, which the skilled man will be able to easily use inorder to meet the essential “main criteria”.

One will understand that it is impossible to provide examples or datafor any type of ultimate composition or ingredient, since theinteractions are complex, so are the kinetics etc. . . . but the skilledman knows about those parameters. According to a less preferred mode,the said PROCESS for preparing the said “cement” compositions or systemsis characterized in the “mixed-treatment” mode by the fact that itcomprises or consists of:

-   -   a) providing a powder of dry, coarse calcium carbonate (s) “low        or medium” filler(s) as defined above    -   b) mixing the said filler(s) with at least an UF to form the        fillers pre-blend    -   c) mixing the said pre-blend with a portion or part of an        efficient treating amount of at least one superplastifier, thus        producing the partially pre-treated fillers pre-blend,    -   d) introducing the said partially pre-treated fillers pre-blend        into a kneading or mixing device already containing mix water or        a composition of mix water possibly containing routine additives        (“mix water composition”) (hereafter for simplicity “mixing        water”)    -   e) introducing before or during step c), preferably during, into        the said kneading or mixing device, the rest of the said        efficient treating amount or proportion of the        superplastifier(s)    -   f) optionally adding before or after the steps c) and d),        preferably before, aggregates such as sand and/or gravel, and        possibly other routine additives not interfering with the said        treatment,    -   g) kneading or mixing the said load during an efficient period        of time    -   h) recovering the said “cement” composition.

According to still another embodiment, the said PROCESS for preparingthe said “cement” compositions or systems is characterized in the“inside-treatment” mode by the fact that it comprises or consists of:

-   -   a) providing a powder of dry calcium carbonate (s) based        filler(s) as defined above    -   b) blending or mixing the said filler(s) with at least one UF,    -   c) introducing the said un-treated fillers pre-blend into a        kneading or mixing device already containing an efficient        treating amount of at least one superplastifier, (or receiving        it just after the introducing of the said un-treated fillers        pre-blend) mix water or a composition of mix water possibly        containing routine additives (“mix water composition”)        (hereafter for simplicity “mixing water”)    -   d) kneading or mixing the said load during an efficient period        of time    -   e) optionally adding before or after the step c), preferably        before, aggregates such as sand and/or gravel, and possibly        other routine additives or adjuvants, not interfering with the        said treatment,    -   f) recovering the said “cement” composition.

By “just after” it is meant that the treating agent can be introducedbefore of after the un-treated filler(s), but in the second case it mustbe introduced rapidly after the filler(s), say, in a matter of someseconds to 10 s or so, in order for the filler to remain fully availablefor the treating agents without any disturbance due to the kneading ormixing with sand, gravel etc.

It is usually most preferred to first introduce the aggregates such assand and gravel into the kneading or mixing device, and mix themoptionally with a small amount of water and/or of fluidifier (seeabove), before performing the other steps.

Efficient”: In the above Process, the term “efficient” means that thetreatment leads to a workable cement composition, according to theself-levelling test or “cone” test, as shown in Table A above, that isleads to a wide diameter of the “galette” AND to a fluid, non sticky,not thick, not “slow”, not “dry”, product as could be seen by “visualinspection”, that is matches the TWO criterias required to reach thequalification as HP or FLUID or TECHNICAL “cement” (in the wide sensedefined above) composition or system.

As discussed above, it will be pure routine for a skilled man to performa few self levelling tests, which are perfectly known to him a requireno costly or voluminous equipment, and no “daunting task”, so as toadapt the dosage of the treating UFs) vs. the filler(s) and/or to definethe moment the treatment can be stopped.

As treatment agent, is used at least one superplastifier (and possiblyat least one superplastifier with possibly some inert amount ofplasticizer for cost control).

As mentioned above, a routine amount of fluidifier can also bepreferably used. According to the above definition of the treatingagent, the so called treating agents for the fillers consist of/orcomprise superplastifier(s), or comprise at least one superplastifier(and optionally at least one plastifier in order to reduce the overallcosts), and preferably consist of at least one superplastifier andoptionally at least one efficiently cost-reducing amount of plastifier,and most preferably one superplastifier and optionally one efficientlycost-reducing amount of a plasticizer.

Superplastifiers are well-known agents and are to the best selectedamong the following products or families and their blends:

Polycarboxylates, polycarboxylate ethers, or much less preferredproducts to manufactured from sulfonated naphthalene condensate orsulfonated melamine formaldehyde. The skilled man knows these products,which are additionally disclosed in the prior art as cited above.

One will use preferably sodium salts of polyether carboxylates which aredisclosed, as well as their preparation, in U.S. Pat. No. 5,739,212.

In this invention, the best mode treating agents (product A and productB) appear to be, in the superplastifiers families, of thepolycarboxylate ether formulae.

Superplastifier(s) and especially Products A and B are disclosed in WO2004/041882.

To be noted, the products codes A to K in Table A are FILLERS to becharacterized, NOT to create a confusion with the preferred treatingagent(s) A and B above which are (superplastifiers(s)).

By “efficient period of time” it is meant here a period of time of about35-65 s for the standard compositions, and from 1-3 to 10-15 min. forthe more “technical” that is more complex and/or more sensitivecompositions, as is known from the skilled man.

For a “standard” (that's is, low or medium) composition, an example canbe a kneading time of 10-15-20 s for the gravel and sand (dry kneadingor mixing is preferred), then of 10 s for the kneading or mixing of thehydraulic binder and untreated filler, then 10-15 s for the kneading ormixing with the treatment agent(s) and mix water (this in the so-called“inside treatment mode”), then 5-15 s for the final kneading or mixingwith the final “routine additives”.

The main and essential criteria for the said “period of mixing” is thatthe final product must be homogeneous and the treating agent(s) be notabsorbed or adsorbed onto the sand or gravel, or the less possibleextent.

By “efficient amount” of plasticizer” (when present with thesuperplastifier) it is meant in this application an amount or proportionof plastifier which is able to reduce the cost of the treatment withoutinterfering negatively with the system and namely the filler(s)behaviour, namely in terms of surface activity and reactivity) the samecriteria applies to the “inert additives”.

By “comprising” we mean here that the said treatment agents consistessentially or entirely of superplastifier(s) as defined, and maycontain as explained a cost-reducing efficient amount of at least oneplastifier, and may also contain inert additives useful for the intendedfinal application, such as anti foam agents, retarders, acceleratorsetc. absolutely known to the skilled man.

Usual additives of inert nature can be added at injection points knownto the skilled man, as said earlier.

The mixing or kneading device can be operated in a batch mode, asemi-continuous mode, or a continuous mode, the adaptations being withinthe easy reach of an average skilled man.

Dosage of Superplastifier(s) Used for the Pre-Treatment and Treatment ofthe Filler(s):

At the end-user location, the dosage in superplastifier(s) is rangingfrom 0.3 to 2-3 kg for 100 kg of cement, preferably 0.8 to 1.2 kg/100 kgof cement, on a DRY/DRY basis.

In laboratory conditions, the same proportion ranges from 0.05 to 0.1%by weight of the carbonate (DRY) that is 0.1 to 0.3 kg/100 kg of cement,on a DRY/DRY basis.

In laboratory conditions, for establishing the Table A, one used from0.8 to 1.2 kg/100 kg cement, on a DRY/DRY basis.

At the end user location, the ratio superplastifier(s)/plasticizer(s)can be from 100/0 to 95/5-90/10, preferably no less than 85/15 on aweight dry basis.

The invention also resides in the said CEMENT (in the broad sense givenabove that is cement, cementitious compositions, mortars, concretes)COMPOSITIONS (OR SYSTEMS) incorporating the said preblend offillers+UF(s) treated with at least one superplasticizer

-   -   per se, since they are distinguishable from the prior art        similar compositions by their physical structure and their        properties,    -   or as prepared by the above process of the invention,    -   as well as compositions (A), (B) or (C) above,        and in the USE of those cement systems or compositions for        making concrete elements,        and ultimately in the CEMENT ELEMENTS incorporating the said        treated pre-blends of low or medium filler+UF    -   per se, since they are distinguishable for the same reasons as        the compositions,    -   and as prepared by using the said compositions. as well as in        the        -   calcium carbonate-based filler(s) as pre-treated by the            pretreatment process of the invention.

Another objective is evidently to meet Client's requirements which arethat the “galette” or “cone” be above 350 mm in diameter, mostpreferably above 4000 mm, or still better, above 420 mm, at acost-effective dosage.

This can be easily and quickly appreciated by a skilled man byperforming the to cone and plate test.

This test allows therefore to discriminate the fillers and UFcombinations, with the assistance of the specification and examples, andthe common general knowledge, and to select the best-performingsuperplastifier(s), in view of the final properties required by the enduser.

The families of superplastifiers are very well known to the skilled man.The merit of the inventors was not to discover those families, nor theiruse as superplastifiers in the common sense of the prior art, but todiscover that one can WIDELY UPGRADE a low-medium filler for cement (andhence the cement compositions) by treating the said the CalciumCarbonate-based filler first with at least one UF then with at least onesuperplastifier.

It has been noted that certain compositions are so low in cone diameter(“self levelling test”), stickiness, etc. that there is no way toupgrade them; this demonstrates the difficulty of the invention's task.

Some can be upgraded but only by adding large proportions of thesuperplastifers used according to the invention and even in such cases,the diameter requirement can be matched, BUT the “galette” or “cone”remains sticky and thick in consistency, what means that the result,despite the fact that the diameter of the “galette” is correct, thecomposition cannot be regarded as upgraded to HP concrete composition.

According to the present invention, the synergistic combination of thesaid low filler with UF(s) prior to the chemical treatment with thesuperplastifier(s) allows to reduce the % of superplastifier treatingagent and hence renders the process cost effective even for such verylow fillers.

It is necessary to keep in mind that, for a concrete composition orsystem to be acceptable as HP composition, or upgraded from low ormedium quality to HP quality, TWO features MUST be met simultaneously:

-   -   the diameter of the “galette” or cone must be above about 350,        or better above 400, or still better above 420 mm, AND    -   the “galette” or cone spreading must NOT be sticky or thick or        dry in consistency, and must feature a correct flow rate.

Most preferably, there should be no exudation or water-release oroutgassing, though some minor such effects can be tolerated when theupgrading is globally impressive.

This is another measurement of the very tough challenge which thisinvention wishes to overcome, and of the very high technical andscientific input brought by the invention to the current state of theart.

As can be seen from the attached Table A, the “poor” fillers can NOT beupgraded since they never meet BOTH features.

This is also true for some “medium” fillers such as product D, B, G, Iand K which may show a good fluidity for example at a dosage of 4 g BUThave a bad aspect or handling behaviour.

With the help of the Table A and of the above and below comments, theskilled man will be able to discriminate the fillers which CAN beupgraded by the invention, and those (regarded as “low” as per the testof the Table A) which can NOT.

To achieve these objectives, the skilled man bears in mind first that acertain water/cement ratio is directly linked to the workability of thecomposition and that it is also imperative to develop high performancequalities in the end product, such as high performance or “technical”level of setting properties, drying properties, mechanical strength,namely compressive strength etc. As specified above, the inventionrelies first on the surface treatment of the CaCO₃-based FILLER(s)+UF(s)pre-blend with one or more superplasticizer(s) (optionally in admixturewith one or more plastifier), and usually in the presence of a routineamount of fluidifier. The amount of plastifier will be calculated easilyby the skilled man as being the efficient cost effective amount, notinterfering with the overall treatment, that is not degrading theresults of the cone test, see above.

Two superplastifiers products which are providing the best results are(as the “best mode” as of the filing date) products A and B of thepolycarboxylate ether family as mentioned above.

It is very surprising to notice that when using the invention,proportions of superplastifier(s) treating agent(s) for the CaCO₃filler(s) as low as 0.03 or 0.05 to 0.1% are sufficient.

It is entirely surprising to notice that such minuscule amounts oftreating agents are capable of upgrading to HP quality even medium topoor fillers. As mentioned above, this is due to a synergy that developsbetween the fillers pre-blend and the superplastifier.

Many such plasticizers, or routine fluidifiers, are known, such asdescribed for example in the CHRYSO patent EP 0 663 892.

Other products have been successfully tested as routine fluidifiersusable in the process of the invention to perform a surface treatment ofthe carbonate filler+UF pre-blend, such as the CHRYSO™ productsdescribed in the above cited EP patent, such as PREMIA 196™, which isreportedly a “modified polycarboxylate” or NRG 100 from Mappei™.

Some usual additives may be routinely added such as air entrainmentagents, setting retarders or accelerators etc. at a place which is knownfrom the skilled man, for example with the water or after thesuperplastifiers are added.

As to the “powders” that is the cement and the fillers pre-blend, thecement can to be added first, then the filler, or the reverse, or theycan be introduced together as a premix.

It is however preferred to introduce the cement and the filler togetheras a premix, so as to better ensure that both powders will behomogeneously mixed with and wet with the water.

The above are batch modes.

One can also think of continuous modes such as performing the additionin one of the above orders, for example in a kneading or mixing deviceequipped with an endless screw (with additions at various points alongthe length of the equipment), possibly with pre-mixes being added atsome point(s), or as another example in a series of successive kneadingor mixing devices, also with the possibility of adding premix(es) in oneof the devices. It will be obvious to the skilled man that especiallythe latter option (several kneading or mixing devices) has numerousdrawbacks, if only the necessary space and investment.

Batch modes are preferred and will be referred to here-below.

Routine tests can help the skilled man to select the most appropriate,in view of the available equipment, of the end user practice, and withthe help of the following Tables and Figure which are attached to thisapplication.

In the following examples, except if otherwise stated, the cement brandis the standardized cement 42.5 R Gaurain (CEM) having a water demand of24.2%, and the sand is Standardized sand under Standard EN 196-1 (SAN).

EXAMPLES Example 1 Betocarb™ SL+UF+Product B

Enclosed is TABLE B showing the tests results.

TABLE B C D E F G J A B Betocarb Betocarb Silica Meta- Etiquette H IChrysoflui K L V-Fun- H2O Cement HP-OG SL fume kaolin violette Sand BPremia 196 Target Results nel (g) (g) (g) (g) (g) (g) (g) (g) (g) (%d/d) (g) (mm) (mm) (sec) standard 243 378 486 0 0 0 0 1350 0 0 3 >350465 5 test 1a 243 378 0 486 0 0 0 1350 1.2 0.1 3 >350 425 7 1.3 0.11 435test 1b 243 378 0 461 25 0 0 1350 1.2 0.1 3 >350 401 8 2.4 0.2 421 test1c 243 378 0 461 0 25 0 1350 1.2 0.1 3 >350 415 8 1.6 0.13 423 test 1d243 378 0 461 0 0 25 1350 0.6 0.05 3 >350 400 7 0.8 0.07 415 1.2 0.1 426test 2a 243 378 0 436 50 0 0 1350 3 0.25 3 >350 423 9 test 2b 243 378 0436 0 50 0 1350 0.8 0.07 3 >350 0 9 1.3 0.11 200 2.1 0.17 436 test 2c243 378 0 436 0 0 50 1350 0.6 0.05 3 >350 425 6 test 3a 243 378 0 411 750 0 1350 3.6 0.3 3 >350 420 12 test 3b 243 378 0 411 0 75 0 1350 2.60.21 3 >350 415 10 2.8 0.23 420 test 3c 243 378 0 411 0 0 75 1350 0.60.05 3 >350 420 6

Also enclosed is Table C showing a summary of the tests, andcorresponding FIG. 1.

TABLE C Betocatb Betocatb SL + 5% Betocatb SL + 10% Betocatb SL + 15%Betocatb SL + 5% Trial SL alone Etiquette viol. Etiquette viol.Etiquette viol. Silica fume No Product % B mm % B mm % B mm % B mm % Bmm 2412/1 Betocatb SL 0.10 425 0.10 426 0.05 425 0.05 420 0.20 421Betocatb SL + 10% Betocatb SL + 15% Betocatb SL + 5% Betocatb SL + 10%Betocatb SL + 15% Trial Silica fume Silica fume Metakaolin MetakaolinMetakaolin No % B mm % B mm % B mm % B mm % B mm 2412/1 0.25 423 0.30420 0.13 423 0.17 436 0.23 420

Betocarb SL is a “low” calcium carbonate based filler (marble)(d50=11-12 microns) (Blaine surface=365 m2/g)

Silica fume SF and metakaolin MK are two UFs as defined above.

Pulverized metakaolin (MK) is made by thermal treatment of natural clay.The crystalline clay minerals are dehydroxylated. Metakaolin powder hasthe higher pozzolanic activity (756 mg CaO/g sample). The calciningtemperature of clay affects the pozzolanic reactivity of the resultingproduct.

Silica Fume (SF)

-   -   Silica fume originates from the reduction of high purity quartz        with coal in electric arc furnaces in the production of silicon        and ferrosilicon alloys and consists of very fine spherical        particles containing at least 85% by mass of amorphous silicon        dioxide.

EV (Etiquette Violette™) is an UF too as defined above, a very finecalcium carbonate from Omey, France, from microcrystalline ChampagneWhiting.

For each group of tests, the UF amount is the same, that is respectively25, 50 and 75 g.

Test 1a is a blank test (no UF)

The amount of mix water remains constant in all tests, 243 g. So is theamount of sand, 1350 g, and water 243 g.

The “standard” test is a comparative test with no UFs but with 486 g ofBL 200 (d50=7 microns, Blaine=462 g/m2) serving as a reference for thecone diameter only (it is a low filler since it gives a poor flow andworkability in the cone test).

Superplastifier B belongs to the preferred family as defined above.

Chrysofluid™Premia 196 is a routine fluidifier and its amount remainsconstant at 3 g.

Table B shows that the low Filler Betocarb HP-OG provides an excellentresult of 465 mm in cone test “galette” diameter (BUT as explainedabove, a poor flow and visual aspect).

When replacing the low filler Betocarb HP-OG with another low fillerBetocarb SL at the same amount of 486 g (test 1a) one reaches 425 mm at0.1% dry weight of superplastifier B or 435 mm at 0.11%.

These Tables B and C show the synergy between the treatment with UF andthat by the superplastifier B.

Example 2 Betocarb SL+UF PCC or UF MCC+B

See enclosed Table D

TABLE D C D A B Betocarb Betocarb E F G H I Chrysofluid H2O Cement HP-OGSL PCC MCC Sand B Premia 196 Target Result V-Funnel Work 2/B (g) (g) (g)(g) (g) (g) (g) (g) (% d/d) (g) (mm) (mm) (sec) A1 243 378 486 0 0 01350 0 0 3 >350 465 6 A2 243 378 0 486 0 0 1350 to adjust to adjust3 >350 435 7 A3 243 378 0 461 25 0 1350 to adjust to adjust 3 >350 422 8A4 243 378 0 436 50 0 1350 to adjust to adjust 3 >350 426 9 A5 243 378 0386 75 0 1350 to adjust to adjust 3 >350 420 10 A6 243 378 0 461 0 251350 to adjust to adjust 3 >350 400 8 A7 243 378 0 436 0 50 1350 toadjust to adjust 3 >350 410 10 A8 243 378 0 386 0 75 1350 to adjust toadjust 3 >350 385 11

This test is the same as above Example 2 except that as UF one uses aprecipitated calcium carbonate PCC d50=1.52 microns, known to be an UF,or a MCC which is a modified calcium carbonate (see USP 6, 666, 953)d50=2.29 microns.

Results call for the same comments as in Example 2.

Example 3 Lavigne+Product A (Comparative Test)

Enclosed is Table E

TABLE E A B C D Reference sample 2252/1 2252/1 2252/1 2252/1 ReferenceLavigne 13μ Lavigne 13μ + Lavigne 13μ + Lavigne 13μ + 0.05% A 0.1% A EVCement 378 378 378 378 H₂O 243 243 243 243 Sand 1350 1350 1350 1350Filler St Béat St Béat St Béat St Béat/Violette CaCO₃ 486 486 486 436/50% A (Sec/sec) 0 0.05 0.1 0 Test 4 g Fluidifier Premia 196 4 4 4 4Consistancy (>350 mm) 413 428 441 440 Aspect A2 A2 A2 A2 ObservationsSlow flow − Slow flow − Slow flow − Fluid mortar + Dilating mortarDilating mortar Dilating mortar somewhat settles

The low filler is Lavigne, a coarse carbonate, marble, d50=13 microns.

The UF used to treat the above filler is Etiquette violette EV d50=2.4microns.

If we consider the lefthand column A (Lavigne Filler with no UFtreatment and no treatment with a superplastifier) we can see that thediameter in the cone test is 413 mm.

Despite the very good value of 413 mm for the diameter of the cone test,the slurry is flowing only slowly and is “dilating”; the overall resultis therefore mitigated since the cone diameter is excellent but the flowtest could be better in visual “aspect”.

Another test has been performed (not shown in the Table) with 3 g offluidifier instead of 4 g: in that case, the mortar becomes “fluid”.

This means that the right optimum in this test is to use the indicatedproportion of EV but between 3 and 4 g of fluidifier, −3.7 g, preferably3.5 g.

If we consider the two central columns, B and C, we can see that bytreating the marble with resp. 0.005% or 0.10% Product A/dry weight ofcement composition one obtains the same “low flow rate” and “dilatingmortar” but with a better diameter.

This shows that the treatment of the considered marble with 0.05 to0.10% Product A improves the workability of the mortar composition, butfor this marble type, not enough.

Below 0.05%, no pertinent measurement of the precise % can be done inLaboratory conditions, so we can see or deduct from the table E that atreatment of this marble with about 0.03 to 0.05-0.10-0.15% Product Bimproves clearly the diameter but not the flow rate.

If we consider now the next column D one can see that by replacing 486 gof Lavigne filler with 436 g of the same Lavigne filler but treated onlywith 50 g of EV according to the invention, with still 4 g of fluidifierChrysofluid Premia 196 being present as above, the cement compositionbecomes fluid with a very high diameter of 440 mm (same as the 441 mmobtained with a treatment with only 1% of Product A) with the onlydisadvantage that it somewhat settles.

Here again, an adjustment of the fluidifier at 3 g instead of 4 grenders the mortar “fluid”.

So, here again, the optimum is a treatment in the presence of between 3and 4 g of fluidifier, such as 3.4-3.7 g, preferably 3.5 g/dry weight ofthe total cement composition.

We can conclude from this table E that the treatment with Product Asuperplastifier alone does not bring, for this specific marble, asolution which is entirely satisfactory. The treatment with only an UFbrings a satisfactory solution at 3-3.5 g fluidifier (it is the subjectmatter of a pending application filed the same day as the present one).

This test confirms the interest of treating the coarse filler first withan UF then treating the preblend with a superplastifier to take benefitfrom the synergy.

Application(s)

The applications are all those commonly using the above describedcement, mortar, or concrete compositions or systems.

Cement Products

Those are the products or elements that are known to be manufacturedfrom the above cement, mortar or concrete compositions, in the buildingindustry or any other industry, in a well-known manner.

1. A product comprising a blend of a course calcium carbonate-comprisingfiller and an ultrafine filler, wherein the blend is treated with atleast one treating agent comprising at least one superplastifier.
 2. Theproduct according to claim 1, wherein the calcium carbonate-comprisingfiller is ground natural calcium carbonate, precipitated calciumcarbonate, modified calcium carbonate, or any mixture thereof.
 3. Theproduct according to claim 1, wherein the course calciumcarbonate-comprising filler has particles having a d₅₀>6 microns.
 4. Theproduct according to claim 1, wherein the course calciumcarbonate-comprising filler is selected from the group consisting of (i)calcium carbonate having a d₅₀ of 7 to 9 microns and a Blaine of 462 to690 m²/g, (ii) calcium carbonate having d₅₀ of 10.4 to 10.8, and (iii)calcium carbonate having a d₅₀ of 18 microns and a Blaine of about 365m²/g.
 5. The product according to claim 1, wherein the ultrafine fillerhas a d₅₀ from 1 to 6 microns and a Blaine of greater than 1000 m²/kg.6. The product according to claim 1, wherein the ultrafine filler has ad₅₀ from 1 to 5 microns and a Blaine of greater than 1000 m²/kg and ofless than 2000 m²/kg.
 7. The product according to claim 1, wherein theultrafine filler is selected from the group consisting of: (i) a silicafume having a d₅₀ of 1 to 2 microns, (ii) metakaolin having a d₅₀ of 3to 5 microns, (iii) metakaolin having a d₅₀ of 3 to 6 microns, a chalkhaving a d₅₀ of 1 to 5 microns, (iv) a calcite having a d₅₀ of about 1micron; (v) white limestone having a d₅₀ of about 2 microns, (vi) amarble having a d₅₀ of 1 to 6 microns, (vii) a marble having a d₅₀ of 1to 5 microns, (viii) ultrafine calcium carbonate having a d₅₀ of 1-2microns, (ix) ultrafine calcium carbonate from microcrystaline whitinghaving a d₅₀ of about 2.4 micron, (x) an utrafine siliceous producthaving a d₅₀ of about 1.86 microns, (xi) modified calcium carbonatehaving a d₅₀ of about 2.29 microns, and (xii) precipitated calciumcarbonate having a d₅₀ of about 1.52 microns.
 8. The product accordingto claim 1, wherein the ultrafine filler is selected from the groupconsisting of: (i) ultrafine calcium carbonate having a d₅₀ of about 2.4microns, (ii) silica fume, (iii) metakaolin, and (iv) ultrafine calciumcarbonate having a d₅₀ of 1 to 2 microns.
 9. The product according toclaim 1, which further comprises water.
 10. The product according toclaim 1, wherein the at least one treating agent comprising at least onesuperplastifier is a superplastifier.
 11. The product according toaccording to 10, wherein superplastifier is a polycarboxylate, apolycarboxylate ether, or a product manufactured from sulfonatednaphthalene condensate or sulfonated melamine formaldehyde.
 12. Theproduct according to claim 10, wherein the superplastifier is apolycarboxylate ether.
 13. A cement composition comprising the productaccording to claim
 1. 14. The cement composition according to claim 13,wherein the superplastifier is present in an amount of from 0.3 to 3 kgfor 100 kg of the cement composition, on a dry to dry basis.
 15. Thecement composition according to claim 13, wherein the superplastifier ispresent in an amount of from 0.3 to 2 kg for 100 kg of the cementcomposition, on a dry to dry basis.
 16. The cement composition accordingto claim 13, wherein the at least one treating agent comprises asuperplastifier only, or a superplastifier and a plasticizer.
 17. Thecement composition according to claim 13, wherein the at least onetreating agent comprises a superplastifier and a plasticizer in a ratioof from 95/5 to 85/15 on a dry weight basis.
 18. The cement compositionaccording to claim 13, further comprising one or more of a fluidifier, asetting accelerator, a setting retarder and an air entrainment agent.19. The cement composition according to claim 13, wherein the coursecalcium carbonate-comprising filler is dry calcium carbonate, the atleast one treating agent is a superplastifier, and the cementcomposition further comprises one or more additives, and optionallywater and aggregates selected from the group consisting of sand andgravel.
 20. A cement product made from the cement composition of claim13.